Catalytic vs. uncatalyzed [2 + 2] photocycloadditions of quinones with alkynes.

Photoreactions of quinones with alkynes under catalytic and non-catalytic conditions were studied. In contrast to recent reports, simple irradiation with blue light is sufficient to trigger [2 + 2] photocycloadditions, which afford either fused cyclobutenes or reactive para-quinone methides (p-QMs) depending on the quinone structure. Revision of the chemo- and regioselectivity of the uncatalyzed photoreactions provided useful insight into their overlooked relatedness to the recently developed catalytic protocols. Experimental evidence indicates that the reactivity of the photochemically generated p-QMs is sufficient to perform uncatalyzed reactions with nucleophiles, which can help to explain the existing transformations and develop new cascade transformations involving quinones and alkynes.

Acid-Catalyzed Cascade Reaction of 2-Alkylfurans with α,ß-Unsaturated Ketones: A Shortcut to 2,3,5-Trisubstituted Furans.

The convergent one-pot method toward trisubstituted furans has been developed. The key transformation behind the synthetic protocol comprises the cascade acid-catalyzed conjugated addition of furans to commercially available or easily accessible α,ß-unsaturated ketones followed by the rearrangement of the intermediate Michael adducts into isomeric furans. The prospect of utilizing the target products as building blocks for the preparation of potential functional molecules for organic electronics has been demonstrated.

Synthesis of (Het)aryl 2-(2-hydroxyaryl)cyclopropyl Ketones.

A simple general method for the synthesis of 1-acyl-2-(ortho-hydroxyaryl)cyclopropanes, which belong to the donor-acceptor cyclopropane family, has been developed. This method, based on the Corey-Chaykovsky cyclopropanation of 2-hydroxychalcones, allows for the preparation of a large diversity of hydroxy-substituted cyclopropanes, which can serve as promising building blocks for the synthesis of various bioactive compounds.